A new polymorph of 2,6-bis­(trifluoro­meth­yl)benzoic acid

Giffin, N.A.; Hendsbee, A.D.; Masuda, J.D.

doi:10.1107/S1600536811011731

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1054

doi:10.1107/S1600536811011731

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A new polymorph of 2,6-bis(trifluoromethyl)benzoic acid

Nick A. Giffin,^a Arthur D. Hendsbee ^a and Jason D. Masuda ^a ^*

^aThe Maritimes Centre for Green Chemistry and the Department of Chemistry, Saint Mary's University, 923 Robie Street, Halifax, NS B3H 3C3, Canada
^*Correspondence e-mail: jason.masuda@smu.ca

(Received 24 March 2011; accepted 29 March 2011; online 7 April 2011)

The asymmetric unit of a second polymorph of the title compound, C₉H₄F₆O₂, contains five independent molecules, which form hydrogen-bonded O—H⋯O dimers about inversion centers. The most significant structural difference between this structure and that of the first polymorph [Tobin & Masuda (2009 ). Acta Cryst. E65, o1217] is the hydrogen-bonded, dimeric orientation of the carboxylic acid functionalities.

Related literature

For the first polymorph of the title compound, see: Tobin & Masuda (2009). For details of the synthesis, see: Dmowski & Piasecka-Macieiewska (1998). For information on dimeric versus catemeric crystal growth in benzoic acids, see: Moorthy et al. (2002 ).

Experimental

Crystal data

C₉H₄F₆O₂
M_r = 258.12
Triclinic, $[P \overline 1]$
a = 10.312 (2) Å
b = 11.243 (2) Å
c = 21.283 (4) Å
α = 79.565 (3)°
β = 88.961 (3)°
γ = 85.125 (3)°
V = 2418.0 (9) Å³
Z = 10
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.14 × 0.11 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.973, T_max = 0.980
16341 measured reflections
8352 independent reflections
5092 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.151
S = 0.85
8352 reflections
771 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.84	1.87	2.701 (4)	172
O4—H4A⋯O10ⁱⁱ	0.84	1.82	2.657 (3)	174
O6—H6A⋯O8ⁱ	0.84	1.84	2.673 (4)	170
O7—H7⋯O5ⁱ	0.84	1.80	2.638 (4)	173
O9—H9⋯O3ⁱⁱⁱ	0.84	1.81	2.644 (3)	174
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011731/pv2403sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011731/pv2403Isup2.hkl

checkCIF report

Comment top

Recent studies on benzoic acids have indicated a potential for selective crystal polymorph engineering. It is suggested that catemeric or dimeric structures of benzoic acids can be influenced by concentration and the presence of solvent (Moorthy et al., 2002). Crystallization from solvent free oil led to the formation of the hydrogen bound, dimeric form of the title compound.

The molecular structure of the title compound is presented in Fig. 1. The most significant structural difference between this structure and the literature polymorph (Tobin & Masuda, 2009) is the hydrogen bound, dimeric orientation of the carboxylic acid functionalities. The five molecules in the asymmetric unit are defined by O—H···O hydrogen bonds ranging from 2.638 (4)–2.701 (4) Å and angles of 170–174° (Tab. 1 & Fig. 2).

Related literature top

Experimental top

The title compound was prepared following the literature methods (Dmowski & Piasecka-Macieiewska, 1998). The compound was crystallized slowly from the resultant oil forming colorless, block-like crystals.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Aromatic hydrogen atoms are removed for clarity.
	Fig. 2. The hydorgen bonding interactions between molecules of the title compound lying about inversion centers. Trifluoromethyl groups and aromatic H atoms are removed for clarity.

2,6-Bis(trifluoromethyl)benzoic acid top

Crystal data top

C₉H₄F₆O₂	Z = 10
M_r = 258.12	F(000) = 1280
Triclinic, P1	D_x = 1.773 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.312 (2) Å	Cell parameters from 4371 reflections
b = 11.243 (2) Å	θ = 2.2–27.4°
c = 21.283 (4) Å	µ = 0.20 mm⁻¹
α = 79.565 (3)°	T = 100 K
β = 88.961 (3)°	Block, colourless
γ = 85.125 (3)°	0.14 × 0.11 × 0.11 mm
V = 2418.0 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	8352 independent reflections
Radiation source: fine-focus sealed tube	5092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −11→12
T_min = 0.973, T_max = 0.980	k = −13→13
16341 measured reflections	l = −25→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 0.85	w = 1/[σ²(F_o²) + (0.0887P)² + 1.2723P] where P = (F_o² + 2F_c²)/3
8352 reflections	(Δ/σ)_max = 0.001
771 parameters	Δρ_max = 0.28 e Å⁻³
6 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₄F₆O₂	γ = 85.125 (3)°
M_r = 258.12	V = 2418.0 (9) Å³
Triclinic, P1	Z = 10
a = 10.312 (2) Å	Mo Kα radiation
b = 11.243 (2) Å	µ = 0.20 mm⁻¹
c = 21.283 (4) Å	T = 100 K
α = 79.565 (3)°	0.14 × 0.11 × 0.11 mm
β = 88.961 (3)°

Data collection top

Bruker APEXII CCD diffractometer	8352 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	5092 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.980	R_int = 0.046
16341 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	6 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 0.85	Δρ_max = 0.28 e Å⁻³
8352 reflections	Δρ_min = −0.29 e Å⁻³
771 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.2018 (2)	0.7426 (2)	−0.03174 (10)	0.0326 (5)
C1	0.1804 (4)	0.6502 (3)	0.08995 (16)	0.0210 (8)
O1	0.5747 (2)	0.5485 (2)	0.55641 (12)	0.0268 (6)
F2	0.0386 (2)	0.7786 (2)	−0.09609 (10)	0.0391 (6)
C2	0.0469 (3)	0.6267 (3)	0.06966 (16)	0.0184 (8)
O2	0.6703 (2)	0.4971 (2)	0.46844 (12)	0.0286 (6)
H2	0.5936	0.4894	0.4581	0.043*
F3	0.0525 (2)	0.88431 (19)	−0.02227 (11)	0.0412 (6)
C3	−0.0026 (3)	0.6834 (3)	0.00950 (17)	0.0207 (8)
O3	0.8142 (2)	0.2255 (2)	0.30586 (12)	0.0256 (6)
C4	−0.1242 (4)	0.6592 (3)	−0.00972 (17)	0.0224 (8)
H4	−0.1558	0.6956	−0.0510	0.027*
O4	0.7566 (2)	0.0674 (2)	0.26430 (12)	0.0263 (6)
H4A	0.8359	0.0441	0.2695	0.039*
C5	−0.1996 (4)	0.5822 (3)	0.03096 (17)	0.0227 (8)
H5	−0.2831	0.5665	0.0179	0.027*
O5	0.5766 (2)	0.2035 (2)	0.86826 (13)	0.0313 (6)
C6	−0.1525 (4)	0.5288 (3)	0.09046 (17)	0.0234 (9)
H6	−0.2049	0.4770	0.1185	0.028*
O6	0.4856 (2)	0.3878 (2)	0.87912 (12)	0.0264 (6)
H6A	0.5603	0.3966	0.8917	0.040*
C7	−0.0301 (3)	0.5491 (3)	0.11012 (16)	0.0186 (8)
F7	0.3484 (2)	0.50617 (18)	0.75965 (11)	0.0366 (6)
O7	0.1849 (2)	0.7599 (2)	0.10138 (12)	0.0250 (6)
H7	0.2624	0.7721	0.1080	0.037*
C8	0.0199 (4)	0.4852 (3)	0.17366 (17)	0.0231 (6)
F8	0.4944 (2)	0.3692 (2)	0.74177 (11)	0.0434 (6)
O8	0.2712 (2)	0.5717 (2)	0.09473 (11)	0.0241 (6)
C9	0.0723 (4)	0.7717 (3)	−0.03502 (17)	0.0269 (9)
F9	0.3243 (3)	0.4099 (2)	0.68321 (11)	0.0577 (8)
O9	0.0663 (2)	0.1576 (2)	0.31237 (12)	0.0244 (6)
H9	−0.0132	0.1803	0.3076	0.037*
F10	0.4166 (2)	0.00770 (19)	0.94653 (11)	0.0433 (7)
C10	0.4828 (4)	0.2792 (3)	0.86606 (17)	0.0233 (8)
O10	0.0096 (2)	−0.0017 (2)	0.27140 (12)	0.0266 (6)
F11	0.4018 (2)	0.17788 (18)	0.98037 (10)	0.0309 (5)
C11	0.3507 (3)	0.2508 (3)	0.84751 (16)	0.0199 (8)
F12	0.2413 (2)	0.0653 (2)	0.99315 (10)	0.0424 (6)
C12	0.2800 (4)	0.1666 (3)	0.88805 (16)	0.0218 (8)
C13	0.1607 (4)	0.1366 (3)	0.87036 (17)	0.0252 (9)
H13	0.1138	0.0803	0.8987	0.030*
F13	0.0824 (2)	−0.0491 (2)	0.41419 (10)	0.0353 (6)
C14	0.1091 (4)	0.1894 (3)	0.81057 (17)	0.0224 (8)
H14	0.0270	0.1691	0.7980	0.027*
F14	0.2542 (2)	−0.1135 (2)	0.46976 (10)	0.0400 (6)
C15	0.1785 (4)	0.2714 (3)	0.76988 (17)	0.0234 (8)
H15	0.1441	0.3064	0.7290	0.028*
F15	0.2106 (2)	0.07786 (19)	0.43794 (10)	0.0370 (6)
C16	0.2977 (4)	0.3034 (3)	0.78793 (16)	0.0217 (8)
F16	0.1837 (2)	−0.03585 (18)	0.15962 (9)	0.0278 (5)
C17	0.3656 (4)	0.3974 (4)	0.74290 (18)	0.0299 (9)
F17	0.1763 (2)	0.14663 (17)	0.17769 (9)	0.0273 (5)
C18	0.3351 (4)	0.1034 (3)	0.95232 (18)	0.0278 (9)
F18	0.3479 (2)	0.07010 (19)	0.13671 (9)	0.0310 (5)
C19	0.0905 (4)	0.0543 (3)	0.29297 (16)	0.0211 (8)
F19	0.6650 (2)	0.7594 (2)	0.45210 (10)	0.0356 (6)
C20	0.2308 (3)	0.0048 (3)	0.30006 (16)	0.0192 (8)
F20	0.8213 (2)	0.6977 (2)	0.39510 (9)	0.0365 (6)
C21	0.3090 (3)	−0.0021 (3)	0.24565 (16)	0.0195 (8)
F21	0.8352 (2)	0.85782 (18)	0.43459 (10)	0.0361 (6)
C22	0.4375 (4)	−0.0487 (3)	0.25249 (18)	0.0223 (8)
H22	0.4903	−0.0511	0.2156	0.027*
F22	0.9052 (2)	0.3168 (2)	0.66535 (12)	0.0454 (7)
C23	0.4900 (4)	−0.0917 (3)	0.31231 (18)	0.0255 (9)
H23	0.5779	−0.1248	0.3164	0.031*
F23	0.7250 (2)	0.4195 (2)	0.67639 (11)	0.0417 (6)
C24	0.4143 (4)	−0.0866 (3)	0.36632 (18)	0.0261 (9)
H24	0.4503	−0.1167	0.4075	0.031*
F24	0.7544 (2)	0.32825 (19)	0.59631 (11)	0.0419 (6)
C25	0.2858 (3)	−0.0376 (3)	0.36039 (16)	0.0202 (8)
F25	0.6092 (2)	0.14615 (19)	0.14326 (10)	0.0337 (5)
C26	0.2081 (4)	−0.0306 (3)	0.42061 (18)	0.0273 (9)
F26	0.7286 (2)	0.28146 (19)	0.16435 (10)	0.0320 (5)
C27	0.2537 (4)	0.0439 (3)	0.18000 (17)	0.0228 (8)
F27	0.6488 (2)	0.26378 (18)	0.41950 (9)	0.0277 (5)
C28	0.6694 (4)	0.5377 (3)	0.52244 (17)	0.0237 (8)
F28	0.4893 (2)	0.1538 (2)	0.44626 (9)	0.0325 (5)
C29	0.8011 (3)	0.5702 (3)	0.54062 (16)	0.0198 (8)
F29	0.6595 (2)	0.07953 (17)	0.40289 (9)	0.0281 (5)
C30	0.8664 (4)	0.5031 (3)	0.59459 (17)	0.0226 (8)
F30	0.5517 (2)	0.3352 (2)	0.11093 (10)	0.0409 (6)
C31	0.9828 (4)	0.5382 (3)	0.61349 (17)	0.0259 (9)
H31	1.0254	0.4930	0.6505	0.031*
C32	1.0379 (4)	0.6378 (3)	0.57941 (18)	0.0255 (9)
H32	1.1180	0.6610	0.5927	0.031*
C33	0.9757 (4)	0.7032 (3)	0.52601 (17)	0.0238 (9)
H33	1.0136	0.7716	0.5023	0.029*
C34	0.8579 (4)	0.6706 (3)	0.50624 (16)	0.0210 (8)
C35	0.7957 (4)	0.7459 (3)	0.44775 (17)	0.0245 (9)
C36	0.8120 (4)	0.3929 (3)	0.63253 (18)	0.0287 (9)
C37	0.7321 (4)	0.1698 (3)	0.28488 (16)	0.0205 (8)
C38	0.5913 (3)	0.2176 (3)	0.28029 (16)	0.0189 (8)
C39	0.5192 (4)	0.2240 (3)	0.33629 (16)	0.0197 (8)
C40	0.3908 (4)	0.2727 (3)	0.33246 (17)	0.0226 (8)
H40	0.3421	0.2763	0.3705	0.027*
C41	0.3330 (4)	0.3163 (3)	0.27363 (17)	0.0238 (8)
H41	0.2454	0.3504	0.2715	0.029*
C42	0.4026 (4)	0.3101 (3)	0.21823 (17)	0.0244 (9)
H42	0.3626	0.3394	0.1779	0.029*
C43	0.5319 (4)	0.2609 (3)	0.22122 (16)	0.0216 (8)
C44	0.6044 (4)	0.2552 (3)	0.16000 (17)	0.0254 (9)
C45	0.5793 (4)	0.1803 (3)	0.40084 (17)	0.0237 (8)
F4	0.1004 (2)	0.38607 (18)	0.16895 (10)	0.0319 (5)
F5	−0.0752 (2)	0.4452 (2)	0.21359 (10)	0.0356 (5)
F6	0.0871 (2)	0.55444 (18)	0.20437 (9)	0.0289 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0198 (13)	0.0469 (14)	0.0305 (12)	−0.0067 (10)	0.0055 (10)	−0.0040 (10)
C1	0.020 (2)	0.0212 (18)	0.0229 (19)	−0.0016 (16)	0.0007 (16)	−0.0061 (15)
O1	0.0138 (14)	0.0371 (15)	0.0322 (14)	−0.0036 (11)	0.0023 (12)	−0.0127 (12)
F2	0.0322 (14)	0.0588 (15)	0.0219 (11)	−0.0052 (12)	−0.0015 (10)	0.0054 (11)
C2	0.0151 (19)	0.0191 (17)	0.0228 (18)	−0.0004 (14)	0.0000 (15)	−0.0084 (15)
O2	0.0157 (14)	0.0436 (16)	0.0324 (15)	−0.0070 (13)	0.0011 (12)	−0.0205 (13)
F3	0.0440 (15)	0.0242 (11)	0.0533 (15)	−0.0063 (10)	0.0131 (12)	−0.0006 (11)
C3	0.014 (2)	0.0228 (18)	0.0271 (19)	−0.0001 (15)	0.0019 (16)	−0.0098 (16)
O3	0.0168 (14)	0.0280 (13)	0.0340 (15)	−0.0026 (11)	−0.0016 (12)	−0.0103 (12)
C4	0.021 (2)	0.0225 (18)	0.0248 (19)	0.0048 (16)	−0.0030 (16)	−0.0092 (16)
O4	0.0139 (14)	0.0247 (13)	0.0415 (15)	0.0025 (11)	−0.0002 (13)	−0.0113 (12)
C5	0.016 (2)	0.0237 (18)	0.031 (2)	−0.0006 (15)	−0.0031 (17)	−0.0123 (17)
O5	0.0164 (14)	0.0317 (14)	0.0505 (17)	0.0031 (12)	−0.0024 (13)	−0.0217 (13)
C6	0.019 (2)	0.0204 (18)	0.031 (2)	−0.0014 (15)	0.0047 (17)	−0.0053 (16)
O6	0.0175 (15)	0.0262 (13)	0.0395 (15)	−0.0010 (11)	−0.0075 (13)	−0.0158 (12)
C7	0.014 (2)	0.0190 (17)	0.0235 (18)	0.0012 (15)	0.0011 (15)	−0.0081 (15)
F7	0.0372 (14)	0.0255 (11)	0.0470 (14)	−0.0088 (10)	0.0025 (12)	−0.0033 (11)
O7	0.0173 (14)	0.0251 (13)	0.0356 (15)	−0.0029 (11)	−0.0036 (12)	−0.0128 (12)
C8	0.0206 (19)	0.0219 (16)	0.0268 (19)	−0.0002 (10)	−0.0001 (13)	−0.0054 (14)
F8	0.0318 (15)	0.0483 (14)	0.0512 (15)	−0.0117 (11)	0.0169 (12)	−0.0099 (12)
O8	0.0149 (14)	0.0250 (13)	0.0333 (14)	0.0007 (11)	−0.0050 (11)	−0.0085 (11)
C9	0.023 (2)	0.031 (2)	0.027 (2)	−0.0001 (17)	0.0004 (17)	−0.0053 (17)
F9	0.080 (2)	0.0733 (18)	0.0228 (13)	−0.0463 (16)	−0.0016 (13)	0.0012 (12)
O9	0.0163 (14)	0.0250 (13)	0.0331 (14)	0.0021 (11)	0.0002 (12)	−0.0104 (11)
F10	0.0571 (17)	0.0273 (12)	0.0453 (14)	0.0187 (12)	−0.0244 (13)	−0.0143 (11)
C10	0.018 (2)	0.0258 (19)	0.030 (2)	−0.0022 (16)	−0.0014 (17)	−0.0157 (17)
O10	0.0163 (14)	0.0281 (13)	0.0383 (15)	−0.0014 (11)	−0.0046 (12)	−0.0135 (12)
F11	0.0327 (14)	0.0293 (11)	0.0320 (12)	0.0006 (10)	−0.0128 (10)	−0.0097 (10)
C11	0.017 (2)	0.0196 (17)	0.0255 (19)	−0.0017 (15)	0.0004 (16)	−0.0102 (15)
F12	0.0482 (16)	0.0463 (14)	0.0290 (12)	−0.0138 (12)	−0.0048 (12)	0.0080 (11)
C12	0.023 (2)	0.0177 (17)	0.0257 (19)	0.0045 (15)	−0.0020 (17)	−0.0081 (15)
C13	0.025 (2)	0.0226 (19)	0.029 (2)	−0.0043 (16)	0.0023 (18)	−0.0062 (16)
F13	0.0236 (13)	0.0486 (14)	0.0326 (12)	−0.0120 (11)	0.0047 (10)	−0.0004 (11)
C14	0.017 (2)	0.0238 (18)	0.029 (2)	−0.0055 (15)	−0.0042 (16)	−0.0088 (16)
F14	0.0439 (15)	0.0475 (14)	0.0246 (12)	−0.0004 (12)	−0.0034 (11)	0.0023 (11)
C15	0.025 (2)	0.0231 (18)	0.0233 (19)	−0.0012 (16)	−0.0055 (17)	−0.0084 (16)
F15	0.0412 (15)	0.0362 (13)	0.0377 (13)	−0.0073 (11)	0.0100 (11)	−0.0167 (11)
C16	0.019 (2)	0.0232 (18)	0.0255 (19)	−0.0037 (15)	0.0017 (16)	−0.0099 (16)
F16	0.0269 (13)	0.0299 (11)	0.0304 (11)	−0.0039 (10)	−0.0054 (10)	−0.0142 (10)
C17	0.029 (2)	0.033 (2)	0.030 (2)	−0.0056 (18)	−0.0006 (18)	−0.0095 (18)
F17	0.0308 (13)	0.0216 (11)	0.0284 (11)	0.0073 (9)	−0.0059 (10)	−0.0055 (9)
C18	0.028 (2)	0.0235 (19)	0.033 (2)	0.0009 (17)	−0.0071 (19)	−0.0080 (17)
F18	0.0270 (13)	0.0392 (12)	0.0258 (11)	−0.0035 (10)	0.0032 (10)	−0.0035 (10)
C19	0.019 (2)	0.0226 (18)	0.0232 (19)	−0.0017 (16)	0.0003 (16)	−0.0074 (16)
F19	0.0186 (12)	0.0465 (14)	0.0371 (13)	0.0052 (10)	−0.0028 (10)	0.0008 (11)
C20	0.019 (2)	0.0149 (16)	0.0247 (19)	−0.0022 (14)	−0.0017 (16)	−0.0056 (15)
F20	0.0402 (15)	0.0470 (14)	0.0243 (12)	−0.0007 (11)	0.0013 (10)	−0.0129 (11)
C21	0.018 (2)	0.0140 (16)	0.0257 (19)	0.0011 (15)	−0.0031 (16)	−0.0038 (15)
F21	0.0414 (15)	0.0264 (11)	0.0381 (13)	−0.0028 (10)	−0.0032 (11)	0.0008 (10)
C22	0.019 (2)	0.0167 (17)	0.034 (2)	−0.0030 (15)	0.0003 (17)	−0.0099 (16)
F22	0.0348 (15)	0.0353 (13)	0.0569 (16)	0.0032 (11)	−0.0033 (13)	0.0139 (12)
C23	0.016 (2)	0.0206 (18)	0.039 (2)	0.0039 (15)	−0.0028 (18)	−0.0049 (17)
F23	0.0372 (15)	0.0417 (13)	0.0444 (14)	−0.0084 (11)	0.0167 (12)	−0.0025 (11)
C24	0.028 (2)	0.0179 (18)	0.032 (2)	−0.0003 (16)	−0.0050 (18)	−0.0028 (16)
F24	0.0456 (16)	0.0279 (12)	0.0536 (15)	−0.0161 (11)	−0.0043 (13)	−0.0044 (11)
C25	0.020 (2)	0.0166 (17)	0.0254 (19)	−0.0055 (15)	0.0000 (16)	−0.0054 (15)
F25	0.0370 (14)	0.0351 (12)	0.0335 (12)	−0.0105 (10)	0.0078 (11)	−0.0152 (10)
C26	0.026 (2)	0.029 (2)	0.027 (2)	−0.0062 (17)	−0.0065 (18)	0.0004 (17)
F26	0.0302 (14)	0.0381 (12)	0.0314 (12)	−0.0174 (10)	0.0097 (10)	−0.0101 (10)
C27	0.021 (2)	0.0201 (18)	0.029 (2)	−0.0013 (16)	0.0031 (17)	−0.0084 (16)
F27	0.0247 (12)	0.0306 (11)	0.0311 (11)	−0.0046 (10)	−0.0071 (10)	−0.0123 (10)
C28	0.019 (2)	0.0261 (19)	0.027 (2)	−0.0002 (16)	0.0002 (17)	−0.0076 (17)
F28	0.0272 (13)	0.0429 (13)	0.0253 (11)	−0.0023 (10)	0.0032 (10)	−0.0008 (10)
C29	0.0131 (19)	0.0220 (18)	0.0270 (19)	0.0010 (15)	0.0011 (16)	−0.0126 (16)
F29	0.0290 (13)	0.0250 (11)	0.0289 (11)	0.0071 (10)	−0.0052 (10)	−0.0048 (9)
C30	0.019 (2)	0.0233 (18)	0.027 (2)	−0.0003 (16)	0.0009 (17)	−0.0093 (16)
F30	0.0473 (16)	0.0472 (14)	0.0243 (12)	0.0005 (12)	0.0010 (11)	0.0015 (11)
C31	0.023 (2)	0.0263 (19)	0.029 (2)	0.0050 (17)	−0.0053 (17)	−0.0077 (17)
C32	0.018 (2)	0.0262 (19)	0.035 (2)	−0.0029 (16)	−0.0033 (17)	−0.0102 (17)
C33	0.019 (2)	0.0214 (18)	0.033 (2)	−0.0039 (16)	0.0060 (17)	−0.0087 (17)
C34	0.021 (2)	0.0201 (18)	0.0233 (19)	−0.0019 (15)	0.0034 (16)	−0.0076 (15)
C35	0.021 (2)	0.029 (2)	0.025 (2)	−0.0047 (16)	0.0023 (17)	−0.0075 (17)
C36	0.023 (2)	0.028 (2)	0.033 (2)	−0.0025 (18)	−0.0043 (19)	−0.0012 (18)
C37	0.019 (2)	0.0220 (18)	0.0214 (18)	−0.0027 (16)	0.0034 (16)	−0.0051 (16)
C38	0.0130 (19)	0.0169 (17)	0.0275 (19)	−0.0016 (14)	−0.0010 (16)	−0.0059 (15)
C39	0.022 (2)	0.0152 (17)	0.0226 (18)	−0.0023 (15)	−0.0023 (16)	−0.0045 (15)
C40	0.019 (2)	0.0215 (18)	0.029 (2)	−0.0015 (15)	0.0029 (17)	−0.0084 (16)
C41	0.017 (2)	0.0233 (19)	0.031 (2)	−0.0004 (16)	−0.0049 (17)	−0.0068 (16)
C42	0.026 (2)	0.0194 (18)	0.027 (2)	−0.0025 (16)	−0.0070 (17)	−0.0023 (16)
C43	0.022 (2)	0.0209 (18)	0.0232 (19)	−0.0049 (16)	0.0019 (16)	−0.0050 (15)
C44	0.026 (2)	0.025 (2)	0.026 (2)	−0.0067 (17)	0.0010 (17)	−0.0023 (17)
C45	0.018 (2)	0.0278 (19)	0.027 (2)	0.0003 (16)	0.0031 (17)	−0.0093 (17)
F4	0.0323 (13)	0.0240 (10)	0.0372 (12)	0.0096 (9)	−0.0095 (10)	−0.0040 (9)
F5	0.0306 (12)	0.0427 (13)	0.0286 (12)	−0.0050 (9)	0.0018 (9)	0.0067 (10)
F6	0.0317 (13)	0.0310 (11)	0.0250 (11)	−0.0016 (9)	−0.0067 (9)	−0.0076 (9)

Geometric parameters (Å, º) top

F1—C9	1.347 (4)	C16—C17	1.503 (5)
C1—O8	1.223 (4)	F16—C27	1.332 (4)
C1—O7	1.305 (4)	F17—C27	1.340 (4)
C1—C2	1.509 (5)	F18—C27	1.341 (4)
O1—C28	1.215 (4)	C19—C20	1.505 (5)
F2—C9	1.339 (4)	F19—C35	1.347 (4)
C2—C7	1.398 (5)	C20—C25	1.399 (5)
C2—C3	1.407 (5)	C20—C21	1.409 (5)
O2—C28	1.310 (4)	F20—C35	1.343 (4)
O2—H2	0.8400	C21—C22	1.384 (5)
F3—C9	1.341 (4)	C21—C27	1.504 (5)
C3—C4	1.389 (5)	F21—C35	1.336 (4)
C3—C9	1.498 (5)	C22—C23	1.380 (5)
O3—C37	1.231 (4)	C22—H22	0.9500
C4—C5	1.386 (5)	F22—C36	1.346 (4)
C4—H4	0.9500	C23—C24	1.384 (5)
O4—C37	1.308 (4)	C23—H23	0.9500
O4—H4A	0.8400	F23—C36	1.338 (4)
C5—C6	1.377 (5)	C24—C25	1.390 (5)
C5—H5	0.9500	C24—H24	0.9500
O5—C10	1.229 (4)	F24—C36	1.330 (5)
C6—C7	1.387 (5)	C25—C26	1.510 (5)
C6—H6	0.9500	F25—C44	1.335 (4)
O6—C10	1.303 (4)	F26—C44	1.347 (4)
O6—H6A	0.8400	F27—C45	1.345 (4)
C7—C8	1.490 (5)	C28—C29	1.511 (5)
F7—C17	1.332 (4)	F28—C45	1.340 (4)
O7—H7	0.8400	C29—C34	1.396 (5)
C8—F5	1.338 (4)	C29—C30	1.404 (5)
C8—F6	1.345 (4)	F29—C45	1.340 (4)
C8—F4	1.350 (4)	C30—C31	1.383 (5)
F8—C17	1.340 (5)	C30—C36	1.497 (5)
F9—C17	1.327 (4)	F30—C44	1.339 (4)
O9—C19	1.305 (4)	C31—C32	1.379 (5)
O9—H9	0.8400	C31—H31	0.9500
F10—C18	1.330 (4)	C32—C33	1.373 (5)
C10—C11	1.500 (5)	C32—H32	0.9500
O10—C19	1.229 (4)	C33—C34	1.392 (5)
F11—C18	1.351 (4)	C33—H33	0.9500
C11—C16	1.398 (5)	C34—C35	1.494 (5)
C11—C12	1.404 (5)	C37—C38	1.503 (5)
F12—C18	1.334 (4)	C38—C43	1.396 (5)
C12—C13	1.379 (5)	C38—C39	1.403 (5)
C12—C18	1.519 (5)	C39—C40	1.387 (5)
C13—C14	1.397 (5)	C39—C45	1.499 (5)
C13—H13	0.9500	C40—C41	1.385 (5)
F13—C26	1.344 (4)	C40—H40	0.9500
C14—C15	1.383 (5)	C41—C42	1.379 (5)
C14—H14	0.9500	C41—H41	0.9500
F14—C26	1.334 (4)	C42—C43	1.397 (5)
C15—C16	1.390 (5)	C42—H42	0.9500
C15—H15	0.9500	C43—C44	1.499 (5)
F15—C26	1.338 (4)

O8—C1—O7	126.0 (3)	C24—C23—H23	120.0
O8—C1—C2	121.5 (3)	C23—C24—C25	120.1 (4)
O7—C1—C2	112.5 (3)	C23—C24—H24	120.0
C7—C2—C3	118.8 (3)	C25—C24—H24	120.0
C7—C2—C1	120.9 (3)	C24—C25—C20	120.6 (3)
C3—C2—C1	120.3 (3)	C24—C25—C26	118.3 (3)
C28—O2—H2	109.5	C20—C25—C26	121.1 (3)
C4—C3—C2	120.2 (3)	F14—C26—F15	106.9 (3)
C4—C3—C9	118.3 (3)	F14—C26—F13	106.6 (3)
C2—C3—C9	121.5 (3)	F15—C26—F13	107.0 (3)
C5—C4—C3	120.4 (3)	F14—C26—C25	111.8 (3)
C5—C4—H4	119.8	F15—C26—C25	111.8 (3)
C3—C4—H4	119.8	F13—C26—C25	112.4 (3)
C37—O4—H4A	109.5	F16—C27—F17	107.1 (3)
C6—C5—C4	119.5 (4)	F16—C27—F18	107.1 (3)
C6—C5—H5	120.2	F17—C27—F18	106.1 (3)
C4—C5—H5	120.2	F16—C27—C21	112.7 (3)
C5—C6—C7	121.2 (3)	F17—C27—C21	111.9 (3)
C5—C6—H6	119.4	F18—C27—C21	111.5 (3)
C7—C6—H6	119.4	O1—C28—O2	125.4 (4)
C10—O6—H6A	109.5	O1—C28—C29	121.2 (3)
C6—C7—C2	119.9 (3)	O2—C28—C29	113.4 (3)
C6—C7—C8	119.6 (3)	C34—C29—C30	118.4 (3)
C2—C7—C8	120.4 (3)	C34—C29—C28	121.1 (3)
C1—O7—H7	109.5	C30—C29—C28	120.4 (3)
F5—C8—F6	106.1 (3)	C31—C30—C29	120.1 (3)
F5—C8—F4	105.6 (3)	C31—C30—C36	118.9 (3)
F6—C8—F4	106.2 (3)	C29—C30—C36	120.9 (3)
F5—C8—C7	112.7 (3)	C32—C31—C30	121.0 (4)
F6—C8—C7	113.6 (3)	C32—C31—H31	119.5
F4—C8—C7	112.0 (3)	C30—C31—H31	119.5
F2—C9—F3	106.6 (3)	C33—C32—C31	119.3 (4)
F2—C9—F1	106.6 (3)	C33—C32—H32	120.3
F3—C9—F1	106.5 (3)	C31—C32—H32	120.3
F2—C9—C3	112.1 (3)	C32—C33—C34	120.8 (3)
F3—C9—C3	111.8 (3)	C32—C33—H33	119.6
F1—C9—C3	112.7 (3)	C34—C33—H33	119.6
C19—O9—H9	109.5	C33—C34—C29	120.2 (3)
O5—C10—O6	125.4 (3)	C33—C34—C35	118.0 (3)
O5—C10—C11	120.7 (3)	C29—C34—C35	121.8 (3)
O6—C10—C11	113.9 (3)	F21—C35—F20	105.8 (3)
C16—C11—C12	118.3 (3)	F21—C35—F19	106.2 (3)
C16—C11—C10	120.6 (3)	F20—C35—F19	105.7 (3)
C12—C11—C10	121.0 (3)	F21—C35—C34	113.0 (3)
C13—C12—C11	121.4 (3)	F20—C35—C34	112.7 (3)
C13—C12—C18	118.1 (3)	F19—C35—C34	112.9 (3)
C11—C12—C18	120.5 (4)	F24—C36—F23	107.2 (3)
C12—C13—C14	119.8 (3)	F24—C36—F22	106.1 (3)
C12—C13—H13	120.1	F23—C36—F22	105.4 (3)
C14—C13—H13	120.1	F24—C36—C30	112.9 (3)
C15—C14—C13	119.4 (4)	F23—C36—C30	112.9 (3)
C15—C14—H14	120.3	F22—C36—C30	111.8 (3)
C13—C14—H14	120.3	O3—C37—O4	124.8 (3)
C14—C15—C16	121.0 (3)	O3—C37—C38	121.1 (3)
C14—C15—H15	119.5	O4—C37—C38	114.0 (3)
C16—C15—H15	119.5	C43—C38—C39	119.0 (3)
C15—C16—C11	120.1 (3)	C43—C38—C37	121.3 (3)
C15—C16—C17	118.6 (3)	C39—C38—C37	119.7 (3)
C11—C16—C17	121.3 (3)	C40—C39—C38	120.0 (3)
F9—C17—F7	107.2 (3)	C40—C39—C45	119.0 (3)
F9—C17—F8	106.7 (3)	C38—C39—C45	121.0 (3)
F7—C17—F8	106.5 (3)	C41—C40—C39	120.5 (3)
F9—C17—C16	112.5 (3)	C41—C40—H40	119.7
F7—C17—C16	111.9 (3)	C39—C40—H40	119.7
F8—C17—C16	111.7 (3)	C42—C41—C40	120.0 (3)
F10—C18—F12	107.9 (3)	C42—C41—H41	120.0
F10—C18—F11	107.1 (3)	C40—C41—H41	120.0
F12—C18—F11	106.6 (3)	C41—C42—C43	120.2 (3)
F10—C18—C12	111.5 (3)	C41—C42—H42	119.9
F12—C18—C12	111.7 (3)	C43—C42—H42	119.9
F11—C18—C12	111.9 (3)	C38—C43—C42	120.2 (3)
O10—C19—O9	125.4 (3)	C38—C43—C44	121.0 (3)
O10—C19—C20	120.9 (3)	C42—C43—C44	118.7 (3)
O9—C19—C20	113.7 (3)	F25—C44—F30	106.9 (3)
C25—C20—C21	118.5 (3)	F25—C44—F26	106.5 (3)
C25—C20—C19	121.1 (3)	F30—C44—F26	106.4 (3)
C21—C20—C19	120.4 (3)	F25—C44—C43	113.2 (3)
C22—C21—C20	120.1 (3)	F30—C44—C43	112.1 (3)
C22—C21—C27	119.8 (3)	F26—C44—C43	111.2 (3)
C20—C21—C27	120.0 (3)	F29—C45—F28	106.4 (3)
C23—C22—C21	120.7 (3)	F29—C45—F27	106.9 (3)
C23—C22—H22	119.6	F28—C45—F27	106.2 (3)
C21—C22—H22	119.6	F29—C45—C39	112.6 (3)
C22—C23—C24	120.0 (3)	F28—C45—C39	111.9 (3)
C22—C23—H23	120.0	F27—C45—C39	112.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.84	1.87	2.701 (4)	172
O4—H4A···O10ⁱⁱ	0.84	1.82	2.657 (3)	174
O6—H6A···O8ⁱ	0.84	1.84	2.673 (4)	170
O7—H7···O5ⁱ	0.84	1.80	2.638 (4)	173
O9—H9···O3ⁱⁱⁱ	0.84	1.81	2.644 (3)	174

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₉H₄F₆O₂
M_r	258.12
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.312 (2), 11.243 (2), 21.283 (4)
α, β, γ (°)	79.565 (3), 88.961 (3), 85.125 (3)
V (Å³)	2418.0 (9)
Z	10
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.14 × 0.11 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.973, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	16341, 8352, 5092
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.151, 0.85
No. of reflections	8352
No. of parameters	771
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.29

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.84	1.87	2.701 (4)	172
O4—H4A···O10ⁱⁱ	0.84	1.82	2.657 (3)	174
O6—H6A···O8ⁱ	0.84	1.84	2.673 (4)	170
O7—H7···O5ⁱ	0.84	1.80	2.638 (4)	173
O9—H9···O3ⁱⁱⁱ	0.84	1.81	2.644 (3)	174

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x−1, y, z.

Acknowledgements

The authors would like to thank the Natural Sciences and Engineering Research Council for a Discovery Grant and a Research Tools and Instruments Grant (JDM), the Canadian Foundation for Innovation for a Leaders Opportunity Fund Grant and the Nova Scotia Research and Innovation Trust (JDM).

References

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